Method of making a chromogen bonded polymer and products thereof



United States Patent 3,344,098 METHOD OF MAKING A CHROMOGEN BONDEDPOLYMER AND PRODUCTS THEREOF Shojiro Horiguchi, Tokyo, and MichieiNakamura,

Urawa-shi, Japan, assignors to Dainichiseika Color & Chemicals Mfg. Co.,Ltd., Tokyo, Japan, a corporation of Japan No Drawing. Continuation ofapplications Ser- No. 232,614, Oct. 23, 1962, and Ser. No. 303,413, Aug.20, 1963. This application Jan. 19, 1965, Ser. No. 427,215 Claimspriority, application Japan, Oct. 31, 1961,

36/38,872; May 6, 1963, BBS/22,546 33 Claims. (Cl. 2641-22) Thisinvention relates to colored polymers. More particularly it relates to amethod of making a novel chromogen-bonded-polymer and compounds madethereby.

This application is a continuation application of applications S.N.232,614 entitled Method of Making Colored Resinous Compositions andCompositions Made Thereby filed October 23, 1962, now abandoned and S.N.303,- 413 entitled a New Reactive Coloring Matter, Processes ForProducing the Same and Processes For Coloring Articles With the Samefiled August 20, 1963.

Generally, paints, inks and coloring materials for textiles andsynthetic resins are made by blending a pigment in dry powder form withsolvents, varnishes, and/ or plasticizers and the like and thendispersing the pigment in the liquid vehicle by wet grinding. However,the pigment particles tend to aggregate or flocculate several timesduring the drying process and to consequently form clusters with aresulting large pigment particle size. Accordingly, such large pigmentparticles are not readily dispersible leading to a low tinting strengththereof.

In an attempt to overcome the disadvantages presented by the aggregationand flocculation of the pigment particles during the drying process, thedispersion of the pigment in the dispersing vehicle has been improved bythe addition of a surface active agent to the vehicle. However, suchaddition while possibly improving the pigment particle dispersion hasproduced undesirable phenomena such as migration.

In any event, since the pigment is merely dispersed in the vehicle suchas in a resin or resin film, properties of the resin such as itsabrasion resistance, hardness, etc., tend to be reduced and thereby tendto invite cracking and delamination.

Accordingly, it is an important object of this invention to provide achromogen-bonded-polymer which is substantially different in chemicaland physical properties from conventional pigment and dyes, which hashigh tinting strength and which is characterized by its good retentionof mechanical and electrical properties.

It is another object to provide a method for making achromogen-bonded-polymer in accordance with the preceding object.

In accordance with the invention, there is provided a method for makinga chromogen-bonded-polymer which comprises the steps of mixing anaddition-polymerizable monomer with a chromogen containing diazoniumsalt of a material selected from the group consisting of dyes, pigmentsand intermediates thereof and polymerizing the monomer by using as apolymerization initiator the diazonium salt to form the aforesaidchromogen-bondedpolymer. There is also provided in accordance with theinvention, the chromogen-bonded-polymer produced by this method.

For a better understanding of the invention together with other andfurther objects thereof, reference is made to the following descriptionand its scope will be pointed out in the appended claims.

Prior to describing the invention in its various particulars, it is tobe realized that the chromogen-bondedpolymer of this invention is achemical compound, i.e. the color forming groups, or chromogens, arechemically bonded directly to the polymer. Consequently, the dispersingproperties and tinting strength thereof are especially good. Inaddition, their resistance to abrasion and their mechanical andelectrical properties are also good.

Essentially, the method of preparing the chromogenbonded-polymercomprises mixing a diazonium salt of a dye or a pigment or anintermediate thereof with mono mers which are addition polymerizable andcarrying out the polymerization by using as a polymerization initiatorthe diazonium salt, which is decomposed with foaming and acts as apolymerization initiator on the mixed monomer to form thechromogen-bonded-polymer.

The diazonium salts which may be used are prepared by diazotizingchromogen containing amino compounds. Pigment type chromogens, which arecharacterized by having no water-solubilizable radical in themselves andwhich are directly bonded to the polymer may suitably include suchvarious well known pigments as phthalocya nine pigment, for example,copper phthalocyanine blue, copper phthalocyanine green, etc., indigopigments, thioindigo pigments, anthraquinone pigments, perinonepigments, perylene pigments, dioxazine pigments, quinacridone pigments,the azo pigment series, such as azo coupling pigments, azo condensationpigments, sulfur pig ments, basic lake pigments and the like. Dye typechromogens which have water-solubilizable radicals in themselves andwhich are directly bonded to the polymer may suitably include achromogen containing a sulfonic acid radical or carboxylic acid radicalon the above-mentioned pigment type chromogen.

Typical further compounds and classes included in the above may betetra-amino copper phthalocyanine blue, tetra-amino chlorinated copperphthalocyanine green, tetra-amino linear quinacridone and the others inthe quinacridone group; 1.4-diamino indanthrene and the others in theindanthrene group, l-diazobenzene-Z-hydroxynaphthoicacid-3-amino-anilide and the others in the azo group, compoundscontaining a sulfonic group or carboxylic acid group on the abovementioned amino compounds. There are other types of amino compounds,which are intermediates of both types of the above-mentioned aminocompounds, such other types being typified by those such as2-hydroxynaphthoic acid-(3'-amino)- anilide. Further advantageouslyuseful diazonium salts in preparing the chromogen-bonded-polymer inaccordance with the invention are copper phthalocyaninebluetetra-diazonium salt, chlorinated copper phthalocyaninegreen-tetra-diazonium salt, linear quinacridone tetra-diazonium salt,indanthrene-1, 4-tetra-zonium salt, l-diazobenzene 2 hydroxynaphthoicacid anilide-3'-diazonium salt, 2-hydroxynaphthoic acidanilide-3'-diazonium salt, and the like.

The above detailed diazonium salts provide the chromogen portion for thechromogen-bonded-polymer.

Monomers that are addition polymerizable that can be used in theinventive process are, for example, vinyl acetate, vinyl chloride,vinylidine chloride, styrene, acrylonitrile, methyl vinyl ketone, methylvinyl ether, vinyl pyrrolidone, vinyl pyridine, isobutylene, maleicacid, fumaric acid, acrylic acid, methacrylic acid and esters thereof,such as the methyl esters, glycidyl methacrylate, acrylamide,diaminovinyltriazine, N,N' -dimethyloldiaminovinyltriazine, N-methylolvinylurea, N-methylol acrylamide, and the like, monomers havingconjugated double bonds such as butadiene, isoprene, and the like, ormonomers having non-conjugated double bonds such as ethylene glycoldiacrylate, diallyl phthalate, N,N'-methylene bis-acrylamide, and thelike.

The above set forth monomers may generally be divided into twosubgroups. A first subgroup thereof consists of a first division whichconsists of addition-polymcrizable monomers which when polymerized forma polymer containing in its structure reactive radicals capable oflinking with a functional group but incapable of cross-linking onitself, such first division suitably including monomers such as maleicacid, fumaric acid, acrylic acid, methacrylic acid, acrylamide,diaminovinyltriazine and vinylurea; and a second division which consistsof addition-polymerizable monomers which when polymerized form a polymercontaining in its structure reactive functional radicals capable ofcross-linking with a functional group, such second division suitablyincluding monomers such as N-methylol acrylarnide, N,N'-dimethyloldiaminovinyltriazine, N- methylol vinylurea, glycidyl methacrylate,allyl-glycidyl ether, diallylphthalate, ethyleneglyco diacrylate,diacrylmethane, and N,N-methylene bis-acrylamide. A second subgroupthereof consists of addition-polymerizable monomers which aredifficultly activated with reactive functional groups, such secondsubgroup suitably including monomers such as vinyl acetate, vinylchloride, vinylidene chloride, styrene, acrylonitrile, methyl vinylketone, methyl vinyl ether, vinyl pyrrolidone, vinyl pyridine,isobutylene, methyl maleate, methyl fumarate, methyl acrylate, methylmethacrylate, ethyl maleate, ethyl fumarate, ethyl acrylate, ethylmethacrylate, butadiene and isoprene.

Diazonium salts of dyes, pigments or intermediates thereof ashereinbefore detailed may be mixed with the aforementionedaddition-polymerizable monomers, and then the mixture is polymerized ina suitable manner to prepare polymers chemically bonded to thechromogen. Polymerization can be carried out by mixing one or more typesof monomers without any regard to ratio of each type of monomer. Theproperties of the polymer portion in the chromogen-bonded-polymer arederived from those of the mixed monomers of various types, i.e.,strongly reactive or non-reactive, or water or oil dispersible, alsodepending upon the ratio of each type of monomer. Such polymerizationcan be carried out by any of the known methods ofaddition-polymerization such as, solution-, block-, emulsionandsuspension-polymerizations. The chromogen-bonded-polymers, i.e. coloredaddition polyrners, are useful by themselves and can also be employed ascoloring agents for other materials.

Because, according to the invention, the chromogen is bonded directly tothe polymer, the resulting chromogenbonded-polymer has particularly gooddispersing properties and tinting strength. In addition, the resistancetoward abrasion is high and no migration is observed. Further, desiredmechanical and electrical properties are substantially preserved.

Additionally, by using polymerizable monomers having functional, i,e.reactive radicals capable of giving a crosslinkage, such reactiveradicals can be introduced into the chromogen-bonded-polymer.

The hereinbelow set forth tabulation is a list of examples of suitablereactive radicals:

Names of Radicals Structure Methylol CH 0H Epoxy -CH-GH2 ChlorohydrinOH-CH CH; Ethyleueimine -N Ethyleneurea -NHC ON Acid chloride -COC1 ()1lYTHn Chlorotriazinc N N or N N 3\ /(3--Cl -(J 3-Gl Ketene -CH=C=O Vinyl-CH=OH2 Isocyanate N=C.=Q

Acid azide -OON Phenylurethane -nnooo@ Malonate added lsocyanate- NHO0CH(CO O R):

Sodium bisulfite added isocyanate -NHO0SO;Na

(sodium sulphoisoeyanate) The monomers having the above-mentionedradicals (functional groups) for forming the chromogen-bondedpolymerhaving reactive (functional) radicals in their structures are in a verywide range. Substantially, the range includes the following largeseparate groups:

(1) Such cross-linkable monomers having methylol radicals which causecross-linking when heated or when an acid catalyst is added, or derivedradicals thereof, such as CH OR and CH SO Na, as for example,N-methylolacrylamide, N,N'-dimethylol diaminovinyl triazine andN-methylol vinyl urea.

(2) Such cross-linkable monomers having epoxy or halohydrin radicalscausing cross-linking when heated or when a basic catalyst orpolycarboxylic acid is added, as for example, glycidyl methacrylate,allyl-glycidyl ether and the like.

(3) Such cross-linkable monomers which will be polymerized when heatedor when a readily decomposable peroxide or diazo compound is added or areducing agent is added as, for example, diallyl phthala-te,ethyleneglycol diacrylate, diacrylmethane and N,N-methylene-bisacrylamide.

This process in accordance with the invention for producing achromogen-bonded-polymer having reactive radicals therein comprisesintroducing a diazonium radical into one of the dyes, pigments andintermediates thereof as mentioned hereinbefore and polymerizing one ormore addition-polymerizable monomers containing one or more monomershaving reactive radicals by using as a polymerization initiator theresulting diazoniurn compound of the chromogen.

With a chromogen-bonded-polymer having reactive radicals thereon, thefixing efficiency thereof may become especially enhanced when they areused for coloring. Thus, if an article to be colored is first treatedwith a dispersion of the polymer in a suitable vehicle and, after suchtreatment, is subjected to an after treatment such as heating, theaddition of a catalyst or a heavy metal, or a variation of pH, thepolymer is rendered insoluble. This is because the after treatmentcauses the reactive radicals to crosslink to a higher molecular weight,i.e., to higher polymer. Consequently, a film of higher polymer willpresent the advantages of greater resistance to solvents and chemicals;of being plasticized within, and thereby will have elasticity; and ofbeing high in abrasion resistance and tensile strength whereby its lifeis greatly prolonged as to cracking and delamination.

The chromogen-bonded-polymer may also contain a reactive radical such asone of those listed in the'hereinbelow tabulated group. These radicalsmay also function as dispersing or solubilizing radicals.

Name of radicals: Structure Hydroxyl OH Mercapto SH Amino NHZ Imino NH-Carboxyl COOH Sulfo SO H Carboamide CONH CONH- Sulfoamide SO NH SO NH-Urea NHCONH NHCONH Ureido CONHCONH- Urethane OCONH Methylene dicarbonylCOCH CO However, if the polymer contains the aforementioned reactiveradicals, which are in themselves solubilizable or dispersible, then thesolubilizing or dispersible radical need not be included. For ahydrophilic radical solubilizable or dispersible in water, at least onepolar radical is properly selected from anionic, nonionic and cationichydrophilic radicals according to the object to be performed by thecoloring matter. As typical thereof, there can be enumerated suchanionic hydrophilic radicals as carboxyl (COOH), sulfate (OSO H) andsulfo (4O H) radicals, such nonionic hydrophilic radicals as hydroxyl(OH), ether (O-) and carboamide (CONH radicals and such cationichydrophilic radicals as amino (NH imino (NH), tertiary amino radicals.For a hydrophobic radical solubilizable or dispersible in oil there isproperly selected at least one nonpolar i group from aliphatichydrocarbon radicals and esters, ether, carboamide, sulfoamide, urea andurethane condensates thereof according to the use desired of theaforesaid coloring matter. I

Processes in accordance with the invention for making achromogen-bonded-polymer having a hydrophilic or hydrophobic radical mayinclude the following:

(1) Introduction of water-solubilizable or dispersible and pyridineradicals.

or to a functional radical of an 6 (a) An amino or imino radical isintroduced by using a lower amine. (b) A pyridinium radical isintroduced by using pyridine hydrochloride. (c) An amino radical isintroduced by using ethylene imine.

(2) Introduction of oil-solubilizable or dispersible radicals.

By using a reactive compound having such hydrophobic hydrocarbon radicalas, for example, a higher aliphatic, or aromatic-amine, alcohol,carboamide, methylol carboamide, isocyanate, urea, urethane or ethyleneurea or a phenolic derivative, the aforesaid hydrocarbon radical isintroduced.

The introduction of the solubilizing or dispersing radical into thechromogen-bonded-polymer enables it to be used in many difierent waysdepending upon the nature of the radical introduced thereinto.

The chromogen-bonded-polymer of the present invention can be utilizedfor different uses depending on the kind of the solubilizable ordispersible radical contained therein, i.e., thechromogen-bonded-polymer into which there is introduced a hydophilicradical can be extensively utilized as a material similar to a dye insuch conventional uses of dyes as dyeing fibrous materials. The polymerinto which there is introduced a hydrophobic radical can be alsoextensively utilized, as a coloring material for paints and printinginks in the conventional uses of pigments.

This is because the chromogen-bonded-polymer of the invention, having inits structure radicals solubilizable or dispersible respectively inwater, organic solvents, plasticizers or and other vehicles, can beeasily dissolved or finely dispersed in such vehicles by merely beingmixed and stirred therein. In the case of the chromogen-bondedpolymerhaving reactive radicals in its structure, when an after-treatment suchas heating, addition of a catalyst or a heavy metal or variation of pHis carried out thereon, the reactive functional radicals of the polymerwill be made to react with each other or with the vehicle so that thepolymer may be cross-linked to be of a higher molecular weight. Thus,its resulting solubilizability or dispersibility will be so negligibleas compared with the molecular Weight of the cross-linked polymer thatit will be able to be made insoluble.

The effects of coloring articles and materials with thechromogen-bonded-polymer having solubilizing or dispersing radicals ascompared with those of conventional dyes and pigments is explained asfollows.

The chromogen-bonded-polymers which have radicals solubilizable ordispersible in oil, for example, have such high dispersibility insolvents and varnishes that when they are utilized as a paint or ink,for example, they will be transparent, high in concentration and havegood spreadability. If the polymers also have the aforesaid reactiveradicals, the latter will cross link to each other article being coatedwith the polymer upon an after treatment of the coated article. If thechromogen bonded polymer is used to color the interiors of synthethicresins and synthetic fibres and a dispersible radical high incompatibility with the resins and/ or fibres is present in the bondedpolymer, the latter polymer will be high in dispersibility and tintingstrength, will cause no migration and will not deleteriously reduce thenormal physical and electrical characteristics of such resins andfibres.

In coloring with conventional water-soluble coloring material such asknown reactive dyes, the chromogens in these dyes are generally chosento have a functional radical which is believed to covalently bond with afunctional radical of the material, such as a fibrous substance, to bebonded to color the material. In this situation, a reactive dye whichhas been hydrolyzed with the water medium or a reactive dye which haslost its functional radicals through reaction with a sizing material,for example, will no longer be able to react with the material to becolored thereby reducing fastness of color. Futhermore, conventionaldyes having a functional radical such as a sulfo or carboxyl radical inits chromogen, if not sufficiently applied to fabric materials, forexample, will again dissolve or disperse in water when the dyedmaterials are washed and will stain white and light colored portions ofthe material. Even where sufficient dye has been applied, variations inpH or other conditions may result in a varying of the hue.

By contrast, when the chrornogen-bonded-polymer produced in accordanceWith the invention has present therein reactive radicals and a radicalsolubilizable or dispersible in water and such polymer is caused toperme ate materials such as fibrous materials in a state having affinitywith water and then the reactive radicals are caused to cross-link witheach other or to react with the functional radical or radicals of thematerials in an after treatment of the materials coated with thechromogenbonded-polymer such as by heating or a pH variation, thepolymer will readily be cross-linked to a higher polymer. The resultinghigher polymer is necessarily s-o insoluble and stable within the coatedmaterials that, even if the materials are washed with hot water, acid oralkali, the color on the material remains fast. Thus it has been foundthat the cross-linked chromogen-bonded-polymer produced by the aftertreatment is so high in its fixing ratio, abrasion resistance and othercharacteristics of fastness that not only cotton, and other cellulosefibres such as viscose rayon and acetate rayon fibres but also wool andsuch synthetic fibres as polyester, polyamide, polyacrylo nitrile andpolyvinyl formal fibres can be uniformly dyed with it.

Where solutions for producing fibres, papers and nonwoven fabrics arecolored with a conventional coloring material, dye, etc., the coloringmaterial will act as an impurity and will deleteriously affect physicalproperties of the colored objects by reducing, for example, theirtensile strength and tearing, bending and abrasion resistance. Bycontrast, the chromogen-bonded-polymer of the invention enhances suchproperties.

In addition, it has been found that when materials and articles such aspapers, textiles, leathers, wooden articles, hard boards, concretewalls, metal plates, glass plates and the like are colored with thechromogen-bonded-polymer of the invention while simultaneously beingresin treated, they are advantageously endowed with the desirableproperty of proof against stain and water, fire and moth damage.

The following examples will serve to illustrate the invention. However,it is to be understood that it is not intended to limit the scope of theinvention thereto. The word parts appearing in the examples is intendedto signify parts by weight.

Example 1 Parts An aqueous solution containing 2% diazotized copperphthalocyanine blue Acrylamide 7 Methyl acrylate 3 Total 100 When thissolution was kept at the room temperature and then heated at 50 C. for10 minutes, addition-polymerization occurred with the evolution offoams. The end point of the polymerization was fixed at a point where nocoloration appears upon the addition of a naphthol -AS alkaline solutionto the above solution. After filtration, 200 parts of methanol wereadded to the filtrate to precipitate the chromogen-bonded-polymer. Thethus-obtained chromogen-bonded-polymer was then dissolved in water andthe hydrogen ion concentration of the aqueous solution was adjusted tothe alkaline side by adding an aqueous solution of 5% Na CO The polymerwas then converted to the methylol compound by reacting therewith 2parts of formaldehyde at 50 C. for 20 minutes. Achromogen-bondedreactive-polyrner solution was obtained.

The following components were then mixed together:

Mineral spirits 64 Total 100 The thus-formed mixture was vigorouslystirred in a homogenizing mixer to prepare an oil-in-Water type ofemulsion for use as a textile printing paste.

This emulsion was printed on a cloth by means of a printing machine,dried on a steam cylinder and heated at 130 C. for five minutes in anair bath to obtain clear blue printed cloth having high resistibilitiesagainst abrasion, washing and solvent.

This example indicates the formation of a chromogcnbonded-polymer, theintroducing into the polymer of a reactive radical, i.e., methylol andthe subjection of a cloth coated with the reactive radical containingchromogen-bonded-polymer to an after treatment of heat to cause a higherpolymerization.

Example 2 per phthalocyanine blue Acrylamide 7 Methyl acrylate 3 Total100 When this solution was kept 10 minutes at a room temperature andthen at 50 C. for 20 minutes, polymerization occurred with continuousfoaming. The end point of the polymerization was fixed at a point whereno foaming occurred and a point where the color of the solution changedfrom greenish blue to sky-blue. After filtration, 250 parts aof methanolwere added to the filtrate to precipitate the chrornogen-bended-polymer.By adding them in open air, blue polymer powder was obtained. Thispowder could be easily dissolved in water to form a clear blue solution.

5 parts of the blue polymer powder which were synthesized according tothe method described above were dissolved in parts of water to make ablue aqueous solution. 3 parts of formalin were added to it andmethylolation was carried out at 65 C. for 25 minutes under thecondition of pH 9 which was regulated by means of adding 5% aqueoussodium carbonate solution.

By adding 300 parts of methanol, a chromogen 'bondedpolymer wasobtained. This polymer was dried in an open air to obtain blue polymerpowder. The blue polymer powder. The blue polymer powder was quitesoluble in water and clear blue aqueous solution was obtained.

This example is similar to that of Example 1.

Example 3 3 parts of unmethylolated blue chromogen-bondedpolymersynthesized according to the first portion of the method described inExample 2 were dissolved in 97 parts of water to make blue aqueoussolution. A quantity of 0.5 parts of melamine and 5.4 parts of formalinwere added to the solution. The pH of the solution was regulated to 7.5by the addition of aqueous sodium carbonate solution. Clear solution wasobtained by then heating at 70 C. for minutes.

After cooling the solution down to 45 C., 0.2 parts of sulfamic acid and2.0 parts of 30% aqueous hydrochloric acid solution were added togetherto the above solution, and then by lowering the pH of the solution to4.5, condensation occurred. After about 10 minutes, by

taking a drop of reactant solution, the condensation degree was detectedby dropping it into a large quantity of cold water and checking thepoint where a. resinous precipitate would be formed.

Then 0.8 parts of aqueous sodium hydroxide solution were added to thesolution which made the pH of the reactant about 10, at which point bluechromogenbonded-polymer solution was obtained. At this state ofprecipitation, nothing could be found when one drop of reactant wasdropped into a large amount of cool water.

To a blue chromogen-bonded-polymer solution which was synthesizedaccording to the method described in this example, 3 times its volume ofmethanol was added,

' whereby blue chromogen-bonded-polymer precipitate was obtained. Thispolymer precipitate was dissolved in water to dilute it to 5% by weightin aqueous solution.

According to the following composition, emulsionpolymerization wascarried out at 55 C. for 1 hr., 65 C. for 4 hrs., and 80 C. for 2 hrs.,with a continuous agitation and heating, and thus colored latex wasobtained.

Parts Blue colored polymer solution mentioned above 75.0

Butyl acrylate 9.5

Vinyl acetate 1.5

Vinylidene chloride 9.0

. Acrylamide 0.2

Sodium phosphate 0.5

Sodium alkyl benzene sulfonate 0.5 Potassium persulfate 0.04 Water 3.76

Total 100.00

Example 4 5 parts of unmethylolated chromogen-bonded-polymer which wassynthesized according to the method described in the first portion ofthe method of Example 2 were dissolved in 95 parts of Water to give ablue colored resinous aqueous solution. 10 parts of melamine and 43Methylolation reaction was carried out at C. after the pH of thereactant Was regulated with 5% aqueous sodium carbonate solution to 7.5.After the complete dissolution was achieved by the addition of 50 partsof butanol and 1 part of phosphoric acid, dehydration reaction wascarried out at 90 C. by circulating the butanol and water, which wasstripped off and collected from the reactant. After the reaction wascompleted, by taking off the excess butanol under a reduced pressure,and by concentrating the reactant to a viscous solution containing ofsolid content, butyl-methylol-melamine type blue resinous solution wasobtained.

Example 5 A mixture was prepared in accordance with the followingformulation:

Into the thus-obtained mixture, 80 parts of an aqueous solutioncontaining 2% of diazotized copper phthalocyanine blue, as explained inExample 1, was added dropwise with stirring and simultaneously thehydrogen ion concentration of this solution was adjusted toward theslightly acid side of neutral with an aqueous solution of 5% Na CO Then,the resulting mixture was kept at room temperature for about 10 minutesand thereafter heated at 50 C. for 20 minutes to carry out thepolymerization. After the neutralization of this solution, achromogen-bonded-polymer was separated by adding 500 parts of methanol.

An aqueous solution containing 20% of the resulting polymer was preparedby adding water to the polymer. The thus-formed chromogen-bonded-polymersolution had very excellent adhesive properties. In a mixture consistingof 15 parts of the above solution and parts of a latex containing acopolymer of acrylonitrile and butadiene, a random web of nylon wassoaked, pressed by a mangle and then dried in a cloth shape to obtain acolored non-woven cloth.

In the same manner as described in Example 1, tetra- (4)-amino copperphthalocyanine green was diazotized to obtain an aqueous solution oftheresulting diazonium salt. Separately, an aqueous emulsion of styrene wasprepared in accordance with the following formulation:

Parts Styrene 40 Polyethyleneglycol alkylether 2 Water 58 Total edpolystyrene product colored uniformly green was proparts of formalinwere added to the colored solution. 7

duced from the above colored resin.

This example illustrates the process of producing achromogen-bonded-polymer having non-reactive radicals.

l 1 Example 7 Tetra-(4-amino) copper phthalocyanine green was diazotizedaccording to the method of Example 2. An emulsion was prepared accordingto the following composition with a strong agitation.

To the thus obtained emulsion, 100 parts of 2% aqueous solution ofdiazotized copper phthalocyanine green were added and polymerization wascarried out for minutes at a room temperature, at 50 C. for 2 hrs. andthen at 60 C. for 2 hrs. By adding 500 parts of methanol to thepolymerization solution, chromogen-bonded-polymer was precipitated.After washing and drying the precipitate, polymer powder was obtained.This powder was quite soluble in esters, ketones and the solution was avery clear green.

parts of glycerine were reacted together with 190 parts of linseed oilin a reaction vessel at 180 C. for 2 hrs. under the circulation ofnitrogen gas. 0.2 parts of zinc acetate and 10 parts of green polymerpowder synthesized according to the method of this example were added inthe form of 60% of xylene solution to the above reaction mixture.

Elevating the temperature to 140 C., gradually, and stripping off themixed vapour of alcohol and xylene, reaction was carried out. Thereaction was then carried out for minutes at 200 C. and thereafter wascontinued for 4 hrs. at 230 to 250 C. with the addition of 60 parts ofphthalic acid. A viscous, alkyd type green solution was obtained.

This example illustrates the formation of a viscous alkyd typechromogen-bonded-polymer having weak reactive radicals, which are stableat room temperature and react with each other at high temperature, i.e.,carboxyl and hydroxyl radicals, and hydrophobic radicals, i.e., aryl andaliphatic hydrocarbon radicals.

Example 8 Styrene monomer was dispersed in the form of an aqueousemulsion as follows:

Parts Styrene 50 Polyethyleneglycol alkylether 1 Water 49 Total 100Parts Polystyrene chip 80 The above-chromogen-bonded-polymer 20 Total100 The mixture was well mixed by a tumbler and polystyrene mold coloreduniformly green was obtamed by feeding the mixture into a pressurizedmolding machine.

This example also illustrates the production of achromogen-bonded-polymer having non-reactive and dispersible radicalsand its use as a coloring moldable material.

While there have been described what are considered to be the preferredembodiments of the invention, it will be obvious to those skilled in theart that various changes and modifications may be made therein withoutdeparting from the invention and it is, therefore, aimed to cover allsuch changes and modifications as fall within the true spirit and scopeof the invention.

What is claimed is:

1. A method of making a chromogen-bonded-polymer which comprises mixingat least one ethylenically unsaturated polymerizable monomer selectedfrom the group consisting of a first division consisting ofethylenically unsaturated polymerizable monomers which, whenpolymerized, form a polymer containing in its structure reactiveradicals capable of linking with a functional group but incapable ofcross-linking on themselves under ordinary curing conditions and asecond division consisting of ethylenically unsaturated polymerizablemonomers which, when polymerized, form a polymer containing in itsstructure reactive functional radicals and capable of crosslinking onthemselves to form a higher polymer and capable of linking with afunctional group of a material colored by said polymer, and a secondsubgroup consisting of ethylenically unsaturated polymerizable monomerswhich, when polymerized, for a polymer containing in its structurenon-reactive radicals incapable of linking either with themselves orwith a compound having functional groups under ordinary curingconditions with at least one species of the diazonium salt of achromogen selected from the group consisting of a first subgroupconsisting of amino derivatives of phthalocyanine pigments,quinacridone, indanthrene pigments, azo coupling pigments, compoundscontaining a sulfonic group on said amino derivatives, compoundscontaining a carboxylic acid group on said amino derivatives and asecond subgroup consisting of amino derivatives of thioindigo,anthroquinone, perinone, perylene, dioxazine, azo condensation, sulfurand basic lake pigments and polymerizing said monomer, said diazoniumsalt of said chromogen being used as the initiator of saidpolymerization to form said chromogenbonded-polymer.

2. A method as defined in claim 1 wherein said first subgroup of aminoderivatives consists of tetra-amino copper phthalocyanine blue,tetra-amino copper phthalocyanine green, tetra-amino linearquinacridone, l-diazobenzene-2-hydroxynaphtholic-3-amino-anilide and 2hydroxynaphthoic acid-2-amino-anilide.

3. A method as defined in claim 1 wherein said first division of saidfirst group of ethylenically unsaturated polymerizable monomers consistsof monomers containing in their structures reactive radicals selectedfrom the group consisting of hydroxy, mercapto, amino, imino, carboxyl,sulfo, carboamide, sulfoamide, urea, ureido, furethano and methylenedicarbonyl radicals.

4. A method as defined in claim 3 wherein said first division of saidfirst group of ethylenically unsaturated polymerizable monomers consistsof maleic acid, fumaric acid, acrylic acid, methacrylic acid,acrylamide, diaminovinyltriazine and vinyl urea.

5. A method as defined in claim 1 wherein said second division of saidfirst subgroup of ethylenically unsaturated monomers consists ofmonomers containing in their structures reactive functional radicalsselected from the group consisting of methylol, epoxy, chlorohydrin,ethyleneimine, ethyleueurea, acid chloride, chlorotriazine, ketene,vinyl, isocyanate, phenylurethane, malonate added isocyanate and sodiumsulfoisocyanate radicals.

6. A method as defined in claim 5 wherein said second division of saidfirst subgroup of ethylenically unsaturated polymerizable monomersconsists of N-methylol acrylamide, N,N-dimethylol diaminovinyl triazine,N-

13 methylol vinyl urea, glycidyl methacrylate, allyl glycidyl ether,diallylphthalate, ethyleneglycol diacrylate, diacrylmethane andN,N'-methylene-bis-acrylamide.

7. A method as defined in claim 1 wherein said second subgroup ofethylenically unsaturable monomers consists of vinyl acetate, vinylchloride, vinylidene, chloride, styrene acrylonitrile, methyl vinylketone, methyl vinyl ether, vinyl pyrrolidone, vinyl pyridine,isobutylene, methyl maleate, methyl fumarate, methyl acrylate, methylmethacrylate, ethyl maleate, ethyl fumarate, ethyl acrylate, ethylmethacrylate, butadiene and isoprene.

8. A method as defined in claim 1 and further includ ing the step ofreacting the chromogen-bonded-polymer with materials containing in theirstructure reactive functional radicals capable of cross-linking to forma higher polymer and of linking with a functional radical of a materialcolored by said polymer to form a chromogenbonded-polymer having saidreactive radicals in its structure.

9. A method as defined in claim 1 and further including the step ofreacting said chromogen-bonded-polymer with materials containingsolubilizing and dispersing radicals in their structures to produce achromogen-bondedpolymer having said solubilizing and dispersing radicalsin its structure.

10. A method as defined in claim 9 wherein said last named materials arematerials capable of introducing into a chromogen-bonded-polymersolubilizing and dispersing radicals selected from the group consistingof carboxyl, sulfate, sulfo, hydroxyl, ether, carboamide, amino, imino,tertiary, amino, pyridine radicals, aliphatic hydrocarbon radicalshaving 2 to 18 carbon atoms, aromatic and cyclic hydrocarbon radicals.

11. A method of making a chromogen-bonded-polymer which comprises mixingdiazotized tetra-(4-arnino) copper phthalocyanine blue with methylacrylate and acrylamide and copolymerizing said acrylamide and methylacrylate to produce said chromogen-bonded-polymer using said diazotizedcopper phthalocyanine blue as the polymerization initiator.

12. A method of making a chromogen-bended-polymer having a methylolradical in its structure which comprises mixing diazotizedtetra-(4-amino) copper phthalocyanine blue with methyl acrylate andacrylamide, copolymeriz ing said acrylamide and methyl acrylate saiddaizotized copper phthalocyanine blue being used as the polymerizationinitiator and reacting the chromogen-bonded-polymer resulting from saidpolymerization with formaldehyde to introduce the methylol radical intothe structure of said polymer.

13. A method of making a chromogen-bonded-polymer which comprises mixingdiazotized tetra-(4-amino) copper phthalocyanine blue with methylacrylate and acrylamide, copolymerizing said acrylamide and methylacrylate said diazotized copper phthalocyanine blue being used as thepolymerization initiator, reacting the chromogenbonded-polymer resultingfrom said polymerization with melamine and formaldehyde to introduce themethylol radical into the structure of said polymer and reacting saidmethylolated polymer with butanol to produce a butyl-methylol-melaminechromogen-bonded-polymer.

14. A method of making a chromogen-bonded-polymer having methylol andsulfo radicals in its structure comprising mixing diazotizedtetra-(4-amino) copper phthalocyanine blue with acrylamide and methylacrylate, copolymerizing said acrylamide and methyl acrylate saiddiazotized copper phthalocyanine blue being used as the polymerizationinitiator, reacting the chromogen-bondedpolymer resulting from saidpolymerization with formaldehyde and melamine to introduce said methylolradical into the structure of said polymer, and reacting saidmethylolated polymer with sulfamic acid to produce saidchromogen-bonded-polymer having said methylol and sulfo radicals in itsstructure.

15. A method of making a chromogen-bonded-polymer comprising mixingdiazotized tetra-(4-amino) copper phthalocyanine blue with methylacrylate, 'glycidyl methacrylate, N-vinyl pyrrolidone and ethyleneglycol monomethylether and copolymerizing said methyl acrylate, glycidylmethacrylate and N-vinyl pyrrolidone said diazotized copperphthalocyanine blue being used as the polymerization initiator toproduce said chromogenbonded-polymer.

16. A method of making a chromogen-bonded-polymer comprising mixingdiazotized tetra-(4-amino) copper phthalocyanine blue with methylacrylate, glycidyl methacrylate, N-vinyl pyrrolidone and ethylene glycolmonomethylether, copolymerizing said methyl acrylate, glycidylmethacrylate ethylene glycol monomethyl ether and N- vinyl pyrrolidonesaid diazotized copper phthalocyanine blue being used as thepolymerization initiator to produce said chromogen-bonded-polymer andmixing a solution of said polymer with a latex containing a copolymer ofacrylonitrile and butadiene.

17. A method of making a latex containing a chromogen-bonded-polymerhaving methylol (and sulfo) radicals in its structure comprising mixingdiazotized tetra- (4-amino) copper phthalocyanine blue with acrylamideand methyl acrylate, copolymerizing said acrylamide and methyl acrylatesaid diazotized copper phthalocyanine blue being used as thepolymerization initiator, reacting the chromogen-bonded-polymerresulting from said polymerization with formaldehyde to introduce saidmethylol radical into the structure of said polymer and mixing anaqueous solution of said polymer with butyl acrylate, vinyl acetate,vinylidene chloride and acrylamide and polymerizing said monomers toobtain said latex.

18. A method of making a chromogen-bonded-polymer which comprises mixingdiazotized tetra-(4-amino) copper phthalocyanine blue with styrene saiddiazotized copper phthalocyanine blue being used as the polymerizationinitiator and polymerizing said styrene to produce saidchromogen-bonded-polymer.

19. A method of making a chromogen-bonded-polymer which comprises mixingdiazotized tetra-(4-amino) copper phthalocyanine green with styrene saiddiazotized copper phthalocyanine green being used as the polymerizationinitiator and polymerizing said styrene to produce saidchromogen-bonded-polymer.

20. A method of making a chrom'ogen-bonded-polymer comprising mixingdiazotized tetra-(4-amino) copper phthalocyanine green withmethylmethacrylate, ethylacrylate and glycidyl methyl methacrylate andcopolmerizing said methylmethacrylate, ethylacrylate and glycidylmethacrylate said diazotized copper phthalocyanine green being used asthe polymerization initiator to produce said chromogen-bonded-polymer.

21. A method of making a chromogen-bonded-polymer comprising mixingdiazotized tetra-(4-amino) copper phthalocyanine green withmethylmethacrylate, ethylacrylate and glycidyl methacrylate,copolymerizing said methylmethacrylate, ethylacrylate and glycidylmethacrylate said diazotized copper phthalocyanine green being used asthe polymerization initiator to form said chromogen-bonded-polymer andreacting said polymer with glycerine, linseed oil and phthalic acid toproduce an alkyd resin type solution of said polymer.

22. The chromogen-bonded-polymer as produced by the method of claim 1.

23. The chromogen-bonded-polymer produced by the method of claim 11.

24. The chromogen-bonded-polymer produced by the method of claim 12.

25. The chromogen-bonded-polymer produced by the method of claim 13.

26. The chromogen-bonded-polyrner method of claim 14.

27. The chromogen-bonded-polymer method of claim 15.

28. The chromogen-bonded-polymer method of claim 16.

29. The chromogen-bonded-polymer method of claim 17.

30. The chromogen-bonded-polymer method of claim 18.

31. The chromogen-bonded-polymer method of claim 19.

32. The chromogen-bonded-polymer method of claim 20.

33. The chromogen-bonded-polymer method of claim 21.

produced by the produced by the 7,637

produced by the 5 produced b h by 10 2:121:21 produced by the producedby the References Cited UNITED DONALD E. CZAJA,

STATES PATENTS Coffman, 260-78 Burk 260-41 Frey et a1. 260-41 Mueller eta1. 260-41 Newman 260-41 Bosshard et a1. 260-41 Sulzer et al. 260-249Iurgeleit 260-41 Skoultchi et a1 260-41 Primkzry Examiner.

produced by the 15 LEON J. BERCOVITZ, Examiner.

R. W. GRIFFIN, Asisistant Examiner.

21. A METHOD OF MAKING A CHROMOGEN-BONDED POLYMER COMPRISING MIXINGDIAZOTIZED TETRA-(4-AMINO) COPPER PHTHALOCYANINE GREEN WITHMETHYLMETHACRYLATE, ETHYLACRYLATE AND GLYCIDAL METHACRYLATE,COPOLYMERIZING SAID METHYLMETHACRYLATE, ETHYLACRYLATE AND GLYCIDALMETHACRYLATE SAID DIAZOTIZED COPPER PHTHALOCYANINE GREEN BEING USED ASTHE POLYMERIZATION INITIATOR TO FORM SAID CHROMOGEN-BONDED-POLYMER ANDREACTING SAID POLYMER WITH GLYCERINE, LINSEED OIL AND PHTHALIC ACID TOPRODUCE AN ALKYD RESINS TYPE SOLUTION OF SAID POLYMER.